DE2253375A1 - CRUMPLING EQUIPMENT WITH AMINOPLASTICS - Google Patents

Description

Anti-crease finish with aminoplasts

The invention relates to means for the high refinement of cellulose content igen textile materials while improving the abrasion resistance, Tear resistance, edge abrasion resistance and edge color resistance, Crease resistance, dimensional stability, permanent folding, easy-care, ironing arm or ironing-free equipment as / ie for Improvement of the wet strength, water absorption and other properties of cellulosic paper. Furthermore, the Invention Processa for the manufacture of finishing agents ,, Process to carry out the finishing of cellulosic Paper and cellulosic textiles as well as processes for the production of clothes from the finished textiles.

The use of easy-care clothing and textiles is constantly increasing because the non-iron, wrinkle-free or

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BAB ORIGINAL

Garments and textiles with a low-iron finish that may have creases and pleats permanently ironed on while remain essentially wrinkle-free after normal wear and little, if at all, iron on after washing have to. These textiles include, for example, the items of clothing designated as easy-care. It is generally known, that the hanger arm or hanger-free finish can be obtained if the textile material is made with thermosetting aminoplasts, also as in US Pat. No. 3,527,558 as curable resins for hanger arm finishing are referred to by textiles, treated and the resins are then cured on the textile material will. The resin treatment is carried out by treating the textiles with an aqueous solution of the aminoplast and an acidic catalyst such as zinc nitrate or magnesium chloride impregnated, dried and the resin by heating or irradiation (for example by irradiation with IR, UV, X-ray, gamma, electron, proton or neutron rays) or is cured by heating in a vacuum, in the latter case the temperature is sufficient to cure the aminoplast must be high after volatile components such as water or formaldehyde have been removed.

In a process known as pre-curing, drying and the curing is carried out continuously, the temperature during drying being below the curing temperature

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door of the aminoplast lies. After drying, hardening follows, whereby the dried, impregnated textiles

\. neither be heated to a temperature sufficient to cure the aminoplast nor by radiation treatment. , ■ ■■ .....

Aminoplasts, i.e. curable resins for hanger arm or hanger-free finishing of textiles, for use in solutions for anti-crease finishing and the manufacture and use of such Anti-crease finishes are known. In general, the aminoplasts are in the form of an aqueous aminoplast solution for anti-crease finish (ACA) on cellulosic textiles applied, these aqueous solutions or suspensions Contain aminoplasts and acidic catalysts. The parts These solutions are generally soluble in water, but the ACA mixtures may also contain other ones Contain ingredients such as wetting agents, fabric softeners, brighteners, swelling agents or chelating agents, some of which are only sparingly or almost insoluble in water, so that the ACA mixtures in the presence of these compounds contain an insoluble phase, i.e. represent a dispersion.

In general, the ACA blend is based on the cellulosic Textile material applied and through a heat treatment, but the temperature is below the curing temperature and / or dried in a vacuum on the normal Peuch-

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Activity content of the textile material ^ under normal conditions corresponding to, for example, 15 to 30 ⁰ C and 15 to 90 % relative humidity. The dried textile material is then further processed by (a) in the case of fibrous, cellulosic textile material, this is spun or woven or processed into fabrics or woven fabrics and, if necessary, shaped into fabric-like nonwoven material, ironed and before or after the weaving into threads or before or after the processing in fabrics, fabrics or non-woven textiles or fleeces is hardened. On the other hand, the dried fiber can also be processed into woven textiles and cured before or after shaping into items of clothing, bed or tablecloths, for example, by (b) in the case of threads they are woven, processed into fabrics or textiles, ironed and before or after further processing are cured into garments or by (c) in the case of fabrics or textiles, these are ironed without creases and cured or processed, ironed and cured into textile articles or garments. After curing, the fabrics or items of clothing can be washed out in order to remove any residues of the uncured aminoplast or other components of the finishing mixture such as catalysts.

If the finishing mixes do not contain a catalyst, they are often grounded as aqueous aminoplastic mixes (AAC) designated. 30 9 8 1 9/1 fH 4

For garments equipped with aminoplasts, namely: The problem of reducing the edge abrasion resistance often occurs in the case of non-iron and easy-care products in particular and the color fastness, the so-called "frosting", on, with a gray-white discoloration on the cracks or edges of the garment exposed to abrasion forms. . '

The previously known finishing process is disadvantageous In addition, that some additives are used in AAC or ACA mixtures to improve the properties the cellulosic textile materials treated therewith develop an unpleasant odor.

The invention is therefore based on the object of equipment ^ - to develop mixtures that do not have the disadvantages indicated.

To solve the problem, an aqueous mixture is proposed which is characterized in that it is an aminoplast, a compound of the general formula I.

(R ¹ XR ² J (R ³ O) C (CH ₀ ) CON (R ^) (R ⁵ ),

12 ·

in which the groups R and R can be the same or different and hydrogen atoms or C to C ^ alkyl groups, R hydrogen

_s 30981971044

atoms, C. to C _r alkyl groups, an SO ^ H group or their

Ii
Salt, χ O or 1, R hydrogen atoms, phenyl, ß-hydroxyethyl or C. to Cg-alkyl groups, R " ⁵ denotes hydrogen atoms, phenyl, hydroxymethyl, ß-hydroxyethyl or C. to Cn-alkyl groups, or in which R and R together with the nitrogen atom form a piperidino, morpholino or pyrrolidin-1-ylinoheterocycle and R in this case denotes a hydrogen atom, and optionally an acidic catalyst suitable for curing the aminoplast and preferably 5 to 75 % by weight of the aminoplast contains.

The textile materials provided with the high refinement according to the invention can be used, for example, as easy-care or non-iron items of clothing and as wrinkle-free and non-iron sheets, Pillows, towels, tablecloths, wall coverings or curtains can be used. The fabrics have a good grip and have an abrasion resistance and tear resistance that is significantly better than when the same cellulosic Textiles are treated with an appropriate aminoplast without the addition of the amide. Papers equipped according to the invention can be used, for example, as paper towels or wet-tear-resistant wrapping paper.

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The aminoplast mixture according to the invention for anti-crease finishing (ACA) contains in an aqueous solution or a aqueous suspension an aminoplast, an acidic catalyst for curing the aminoplast and an effective amount of the amide; if necessary, the ACA mixture can also contain other auxiliaries, such as brighteners, Fabric softeners, wetting agents, swelling agents or chelating agents. The mixture can be caused by heating or by irradiation to be cured. . .

By using the claimed amides in ACA mixtures develop treated, dried and hardened TU-rather, Garments and curtains have a better grip $ a better abrasion resistance, better wrinkle resistance, better tensile strength, excellent shrink resistance and an essential improved edge abrasion resistance compared to textile material, which has been treated with the ACA mixture containing no amide. . ·

In addition to ACA mixtures, aqueous ones can also be used according to the invention Aminoplastmischungen (AAC) produce, which an aqueous solution or aqueous suspension with an aminoplast and an effective Represent the amount of amide and optionally with the above-mentioned additives, these mixtures essentially are free of acidic curing catalysts, The AAC- '

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Mixtures can be made by irradiation or by heating in Cured in the presence of an acidic catalyst such as sulfur dioxide, hydrogen chloride or hydrogen bromide will.

Even when using AAC mixtures containing Amides are the dried and hardened cellulose-containing textile materials such as fabrics and clothing that are treated with them and curtains with a much better grip, better abrasion resistance, better crease resistance, greater tensile strength, excellent shrinkage resistance and significantly improved edge abrasion resistance in comparison to corresponding textiles after a treatment with an AAC mixture without an amide content.

The cause of these surprising improvements has not been clarified and is in contrast to previously known considerations, since, for example, in US-PS 3 IM 299 is given, that a finishing agent for cellulosic textiles must have at least two or more methylol groups per molecule, while, in contrast, the amides used according to the invention never have more than one methylol group per molecule and often contain no methylol groups at all.

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A process for crease-resistant equipment and for generating Bügelarm- or non-iron properties are, for example, 3 434 79 ¹ ^ 2 974 432, 3,533,728, 3 L8L 927, 3518044, or 3531 8O6 known from the US-PS 3,526,474 to which is hereby referred to,

The use of liquid aminoplast solutions to improve the physical properties of paper is also known, whereby ACA or AAC mixtures are often used in paper finishing are referred to as aqueous aminoplast paper treatment agents or as aqueous aminoplast paper treatment mixtures.

The mixtures used according to the invention can contain considerable amounts of up to, for example, about 50 % _3, in particular about 10 to 20 %, of at least one water-soluble but non-aqueous solvent, such as, for example, dioxane, acetone, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, dimethylformamide or Dimethyl sulfoxide.

The invention thus relates to aqueous mixtures with a content on aminoplasts and an amide compound of the general formula I '- *

(R ¹ ) (R ² ) (R ³ O) C (CH ₀ ) COiI (H ⁴ ) (R ⁵ ) _β

d ' χ

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1 2
in which the groups R and R are identical or different

can and hydrogen atoms or C. to C _r . Alkyl groups and in which R is a hydrogen atom, a C. to C, alkyl or -SO ^ H group or its salt, χ 0 or 1, R is a hydrogen atom or a phenyl, ß-hydroxyethyl or C ₁ to Cg-alkyl group and R a hydrogen atom, a phenyl, hydroxymethyl, β-IIydroxyäthyl- or C ^ to Cg-alkyl group, where R and R together with the nitrogen atom can form a piperidino, morpholino or pyrrolidin-1-ylinoheterocycle , and where R is a hydrogen atom,

¹ J 5
when R, R and the nitrogen atom form a heterocycle.

At least some of the amides can form acidic addition salts, which general formula I above covers them accordingly.

The mixtures containing essentially no acidic reacting catalyst for curing the aminoplasts, i.e. AAC mixtures, are prepared in such a way that the pH of a mixture is mixed with a sufficient amount of an aminoplast precursor based on the aminoplast content in the final mixture , aqueous formaldehyde with preferably about 20 to 50 % formaldehyde, optionally additional water and a sufficient amount of a compound of the general formula I is adjusted to about 8.5 to 10.5, the equivalent ratio of aminoplast precursor to formaldehyde about 1: 1 / 1 to 2 and preferably about 1: 1.25 to 1.57 and, if necessary, the volume of the mixture is adjusted so that the AAQ mixture is about 20 to 80 % and preferably 30 to 50 %

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Contains aminoplast. The adjustment of the pH, by addition of (1) alkali hydroxides, (2) barium _s (3) sodium carbonate and / or potassium carbonate ⁽¹ L) of sodium hydroxide and sodium carbonate and / or potassium carbonate, or (5) of potassium hydroxide and potassium carbonate and / or Sodium carbonate take place, whereby for reasons of solubility neither barium hydroxide nor lithium hydroxide should be used together with sodium carbonate and / or potassium carbonate. The mixture with adjusted pH is then heated to about ¹ JO to 90 ⁰ C and preferably 60 to 70 ° C during a period of 30 to 2 * 10, and preferably 60 to 120 minutes, whereafter the pH of the mixture by Adding acids such as sulfur: - acid, acetic acid, formic acid, hydrochloric acid or phosphoric acid is adjusted to 6.5 to 7. Suitable aminoplast precursors are, for example, melamine, urea, ethylene urea, dihydroxyethylene urea and / or propylene urea. ■■;

The mixtures essentially free of acidic catalysts but can also be made by a mixture of Aminoplast precursor, water, ammonia and a compound of the general formula II

(H ¹ ) (Λ (HO) C (CH *) J3.OQH $>: '

12 · G

in which R, R and χ have the meaning given above and R is a C>, - to C ^ -alkyl group, to about 20 to 10Q ⁰ C while '

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for a period of time from 0.25 to 24 and preferably k to 6 hours, the molar ratio of the compound of the general formula II to ammonia being 1: 1-10 and preferably 1: 2-5. The mixture is then freed from unreacted ammonia by heating it to boiling or under reduced pressure to vigorous boiling or, if necessary, treating it with an inert purging gas such as nitrogen, argon or helium introduced by a bubbler during the heating and mixing it with aqueous ammonia solution, the The equivalent ratio of aminoplast precursor to formaldehyde in the mixture can be adjusted to about 1: 1.1-2 and preferably 1: 1.25-1.57 and the pH of the mixture can be adjusted to 8.5 to 10.5. The mixture is then preferably maintained such as 0.25 to 2k, usually 0.25 to ¹ J 1.5 to 3 hours at a temperature of about 25-190 ⁰ C and preferably 90 to 18O ° C in a closed vessel, after which the pH of the mixture is adjusted to 6.5 to 7. Preference is given to using compounds in which, in the general formula II, x = 0, R and R are methyl groups and R is a hydrogen atom.

Mixtures containing an acidic curing catalyst, ie ACA mixtures, can be used in a simple manner by mixing the AAC mixtures with an effective amount of an acidic curing catalyst.

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Frequently used aminoplasts for anti-crease finishing and / or acidic catalysts for catalyzing the curing of the aminoplast components and processes for carrying out the finishing are for example in US Pat. Nos. 2,974,432, 3,138,802, 2,357,273, 3,181,927, 2,887-409 , 3,450,485, 3,144,299, described 3,527 and 3,531,806. Aminoplasts used with preference are di- and poly-N-methylol-, N-methoxymethyl- and other N-lower-alkoxymethyl derivatives of urea, cyclic ethylene urea, alkyl triazone, cyclic propylene urea, cyclic 4,5-dihydroxyethylene urea, alkyl carbamates. Urons and thiourea. Suitable compounds are also dimethylol-propyleneurea, dimethylol-ethyleneurea, polymethylol-melamines, formaldehyde-imidazolinone adducts, mixtures of dimethylol-imidazolinone-2 and its' water-soluble ethers, methylol derivatives of 4,5-dihydroxy-imidazolidone, 1,3-dimethyl-4 , 5 ~ dihydroxy-2-imidazolinone, alkyl-substituted 4,5-dihydroxy-2-imidazolidinones, reaction products of dimethyloldihydroxyethylene urea and p-dioxane, 1,3-dimethylol-4,5-bis- (alkoxy) -2-imidazolidinones, l, 3-bis- (hydroxymethyl) -2-imidazolidone, imidazolidinone-aminoplast mixtures, 'reaction products of urea, glyoxal and formaldehyde, polyalkylated monoureins, alkylated urone resins mixed with melamine-formaldehyde-

Resins, N, N ¹ -dimethyloluron-dialkylate and formaldehyde-urea resins, alkylated urone resins and triazone mixtures, amine-modified urone resins, N ₁ N ¹ -bis (acyloxymethyl) -urons,

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-Ik-

N, N'-bis- (methoxymethyl) -uron-formaldehyde adducts, N, N'-bis- (methoxymethyl) -uron-formaldehyde adducts and reaction products, urea-formaldehyde condensates, dicyandiamide-urea-formaldehyde condensates, Mixtures of monomeric and polymeric urea-formaldehyde condensates, 2-hydroxyethylamine-urea-formaldehyde condensates, amine-modified cyclic urea resins, polymethylolureas with a high formaldehyde: urea ratio, Aminoethanol-urea-formaldehyde resins, high grade alkylolated nitrogen compounds or cyclic amide condensates from diketones and dialdehydes. Most of these aminoplasts are water soluble.

Aminoplast precursors are known compounds, mostly amines or amides, which are found in a basic or weakly acidic medium react with formaldehyde, so that when the pH is adjusted to an almost neutral value such as 6.5 result in up to 7 aqueous aminoplast mixtures. Suitable compounds are, for example, urea, biuret, melamine, and others Triazines, ethylene urea, propylene urea, alkyl carbonates, thiourea, 4,5-dihydroxyimidazolidones, 1,3-dimethyl-'J, 5-dihydroxy-2-imidazolidones, alkyl-substituted ^, 5-dihydroxy-2-imidazolidinones, alkyl carbamates or triazine resins.

Preferred catalysts are zirconium, aluminum, lead, manganese, cupric and zinc acetate, zinc nitrate, magnesium

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chloride, zinc aluminum nitrate, zinc fluorate, zinc perchlorate and -chloride, magnesium chloride, magnesium chloride / formic acid, Magnesium chloride / citric acid, ammonium salts of sulfonic acids, ammonium salts of phosphoric acids and volatile acids such as Hydrogen chloride, hydrogen bromide and sulfur dioxide.

The concentration of the aminoplast and the acidically reacting catalyst in the ACA mixture and the concentration of the aminoplast in an AAC mixture are not factors influencing the invention. Preferably, however, the aminoplast solution or dispersion should be in the form in which it is applied to the cellulosic textile materials, ie as a mixture of aminoplast, water, optionally water-soluble solvents. Amides, in the case of the ACA mixture catalysts and optionally brighteners, fabric softeners and chelating agents, about 5 to 50 % such as 2 ₃ 5 to 50 % y mostly 5 to 30 % and preferably 10 to 30 % of the aminoplast and 0.25 to 10 % and preferably 0.5 to 6 % of the catalyst in the case of an ACA mixture.

Suitable wetting agents are, for example, sodium lauryl sulfate, Sodium dioctyl sulfosuccinate, sodium läuroyl sarcosinate, Alkyl phenyl polyoxyethylene glycols and the sodium or potassium salts high molecular weight alkyl sulfates or sulfonates.

Suitable chelating agents are sodium or potassium ethylenediamine tetraacetate, Sodium or potassium nitrilotriacetate and sodium ß-hydroxyethyl ethylenediamine triacetate. As a brightener can, for example, bistriazinyl derivatives of 4, V-diaminostilbene-2,2'-disulfonic acid or derivatives of naphthotriazolyl-stilbene-sulfonic acid can be used.

Polyethylene emulsions, Acrylic acid emulsions, silicones, wax emulsions, fluorocarbons, chromium salts of higher fatty acids, sulfonated oils, sulfated Fatty alcohols or quaternary ammonium salts are added.

The known swelling agents for cellulose are inorganic or organic compounds such as dimethyl sulfoxide, Dimethylformamide, dimethyl sulfone, lithium thiocyanate and calcium chloride and bromide.

These auxiliaries can be added in various amounts without impairing their effectiveness.

Compounds of the general formula I in which R ^ is a hydroxymethyl group is, can by reacting a compound of the general formula I in which R is a hydrogen atom with aqueous formaldehyde in the presence of a base such as

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Barium hydroxide prepared and the resulting methylene compound added to the other ingredients of an ACA mixture. If necessary, these compounds can also be formed in situ, in which case the pH value during the formation of the methylol compound should preferably be above 7, in particular around 8.5 to 9> 5, in an environment with an excess of formaldehyde content. "However, an acidic medium such as pH 5.0 to 6.9 and in particular 5.5 to 6.5 is preferred if the aminoplast is dimethylol-dihydroxyethylene urea. After the methylol compound has been formed in situ, the pH can optionally adjusted to about 6.5 to 7, so that an AAC mixture is then converted into an ACA mixture by adding an acidic catalyst.

N-methylol lactamide (CH) (HO) CHCONHCH ₂ Oh is a known compound which is described by Einhorn et al., Ann. 19O8 _r 361, 113 »Beilstein, 1921, III, 283, CA 1908, 2, 2682, by reacting lactamide and formaldehyde solution in the presence of barium hydroxide. Other N-methylol compounds can be obtained by this process if, instead of the lactamide, a suitable amide with an active hydrogen atom on the amide nitrogen is used.

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The concentration of a compound of the general formula I in the mixtures according to the invention can be varied within wide limits and still gives excellent results. In general, a concentration of from about 0.5 to 35 % and in particular from about 2 to 10 % _f, based on the total weight of the mixture, is preferred.

Good results were also obtained, for example, when the mixtures contained compounds of the formula I in concentrations above 35 % ; However, since there is no longer any significant technical advantage when using concentrations above 25% , the use of such highly concentrated solutions is economically unfavorable. If the mixtures contain less than 0.5% of the compounds, the results are still favorable, but these are somewhat less good, in particular with regard to the handle, the abrasion resistance, tensile strength, tear strength and shrinkage, than when solutions with a content of at least 0 , 5 % are used. The concentration required in a certain mixture to achieve optimal results, for example for treating a certain cellulosic textile material for the production of easy-care or non-iron shirts made of cotton fabric or mixtures of cotton and polyester fibers can be determined in a simple manner.

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It is known that some anti-crease finishes are based on of aminoplasts an addition of acid such as acetic acid ", sulfuric acid, formic acid or phosphoric acid need to lower the pH value of an ACÄ mixture, before these mixtures can be cured by heat or heat and vacuum. This also applies to the ACA mixtures of the present invention.

The finishing mixtures according to the invention can optionally more than one aminoplast and / or more than one compound of the general formula I.

The mixtures according to the invention are stable. Possibly Thus, a cellulosic textile material can be impregnated with the mixture, dried and placed in a storage room before curing stored or transported to a further processing plant. The storage stability is generally at least three months. Impregnated and dried, but not hardened fabrics can be rolled up and stored or shipped in the form of a bale of fabric. Possibly grains containing cellulose Textile materials also impregnated with a mixture according to the invention, dried and before curing with a Aldehyde stored or transported. The storage stability is about six months. In this case, too, substances can be used after impregnation and drying and before hardening

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are stored or shipped with aldehydes in the form of rolls or balls of cloth.

Preference is given to compounds of the general formula I

1 2 * ΐ

sets, in which (a) x = 0, R is a methyl group and R to R ³

Hydrogen atoms, (b) x = 0, R a methyl group, R, R and R hydrogen atoms, R a -SO, group and R (- a hydrogen atom or a hydroxymethyl group, or (c) in which x = 0, R ₁ a methyl group, R, R ^ and R hydrogen atoms and R, - mean a hydroxymethyl group.

The mixtures according to the invention can be used for wetting cellulosic textile material so that this material contains 10 to 100 % and preferably 10 to 60 % of the mixtures. The moist textile material can then be dried and then cured by heating or irradiation with, for example, IR, UV, X-ray, gamma, electron, neutron or proton beams.

Before finishing with the mixtures according to the invention, the textile material is preferably bleached and desized.

Cellulosic textile material can also be mixed with without a significant content of acidic catalysts are treated; in this case the material is impregnated, dried

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and then either by irradiation with, for example, IR or UV rays or with high-energy radiation such as X-rays, gamma, electron, proton or neutron rays or by heating in the presence of an acidic catalyst such as hydrogen halides such as hydrogen chloride or hydrogen bromide, sulfur dioxide or formic acid vapors at a temperature of over 25 ^° C., preferably about -50 to 65 ° C., for a time of 0.5 minutes to 1 hour according to US Patents 3,518,044 and 3,450,485.

Cellulose-containing textile material can be made crease-resistant by impregnating with an effective amount such as, for example, 25 to 100 % of a mixture containing 1 to 40 and preferably 5 to 20 % of a compound of the general type. Formula I, subsequent drying of the material, and · j hardening of the mixture using an aldehyde such as formaldehyde, glyoxal, acrolein or their homologues according to the method of US Pat and 'an effective amount of a gaseous acidic catalyst such as hydrogen chloride,

Hydrogen bromide, hydrogen iodide, sulfur dioxide or formic acid vapors or through; ®e ^ radiation mrt high-energy rays take place in the presence of formaldehyde. Formaldehyde can be used in common Way by evaporating an aqueous formaldehyde solution.

309819/1044 ^; " ⁴

by heating paraformaldehyde or by heating trioxane, preferably in the presence of a catalyst such as boron trifluoride or another cationic catalyst, getting produced. With this method, in particular, the physical properties, and preferably affect the wet tensile strength and the rate of water absorption of cellulosic paper favorably.

Optionally, the cellulose-containing textile materials with an aqueous aminoplast mixture, an ACA mixture, which contains an effective amount of an acidic catalyst, by immersing the material in the mixture, drying the impregnated material and curing the aminoplast for a time of 1 to 30 minutes be, and preferably 2 to 15 minutes at temperatures of 120 to 2o5 ° C and treated, preferably 150 to 200 ⁰ C. Curing can be accelerated if necessary by applying a vacuum. In addition, the curing can also be carried out by irradiation.

The quality of paper, especially its wet tensile strength, Wet abrasion resistance, wet tensile strength and water absorption can be improved by impregnating the paper with an AAC mixture, Drying the impregnated paper, and curing the dried impregnated paper by irradiation or by

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Heating can be improved. Such an improvement can also be achieved by treating the paper with an ACA mixture containing 0.1 to 5 % of an acid catalyst, drying the impregnated paper and curing the dried impregnated paper by heating. The papers pretreated in this way can be used, for example, as paper towels, as absorption papers with high water resistance or filter papers.

By impregnating a fabric with a mixture according to the invention containing acidic catalysts, drying the impregnated fabric at a temperature below the curing temperature of the aminoplaöt constituent of the mixture, cutting the dried fabric in a certain shape and sewing a garment, creating creases in the finished garment and subsequent heating of the item of clothing to harden the aminoplast, with the aminoplast in situ changing to the insoluble state, ready-made 'finished items of clothing' can be produced from cellulose-containing textile materials. Curing may either by irradiation or by heating at, for example, 120 to 2o5 ° C and are preferably carried out at 150 to 200 ⁰ C. If curing takes place by irradiation, no acidic catalyst need be present; if acidic catalysts are nonetheless present, they certainly do no harm.

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The garments produced in this way are non-iron and the gaps once created are also after repeated washing of the garment is not affected.

Under the term equivalent of an aldehyde or an aldehyde-releasing one Compound in the description is understood to mean that amount of an aldehyde or an aldehyde-releasing compound which has 1 g of formula weight, i.e. 29> 19 g Contains or can form -CHO groups. One equivalent of formaldehyde therefore means 1 mole of formaldehyde, while 1 equivalent Trioxane as a formaldehyde-releasing compound means 1/3 mol of trioxane.

The equivalent of an aminoplast precursor is understood to mean that amount of the precursor that is equivalent to one Aldehyde such as formaldehyde can react. Taking one equivalent of an amide such as lactamide is the amount of amide understood with an equivalent an aldehyde such as formaldehyde can react.

Cellulosic textile material refers to textile fibers or mixtures of at least two textile fibers, threads or Mixtures of at least two threads, multiple threads or yarns or substances understood that are woven or non-woven, knitted, folded or otherwise shaped, this

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Textile material has 20 to 25 % or more of a cellulose-containing component which is cotton, cotton linters, mercerized cotton, linen, ramie, jute or regenerated cellulose such as viscose or cuprammonium rayon
can. The non-cellulosic components of the textile material can be other natural or synthetic components, such as wool, silk, acetatrayon, polyamides, polyester or acrylic polymers. ■,.

In the description and in the claims, a cellulosic textile material or a cellulosic paper is referred to as dry, if this material is still so much water
contains, as it would also contain if the textile material or paper is dried in normal air in a normal room, such as at 15 to J> 0 C and at
a relative humidity of 10 to 90 %

Unless otherwise stated, all partial and
Percentages based on weight.

An effective amount of an aminoplast is understood to mean that amount which, when the mixture is used for impregnating a cellulose-containing textile material and after
Drying and curing of the "impregnating material" this
ürid makes wrinkle-free ^; thus. to easy care properties, ironing

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free properties and excellent permanent folding properties leads. Depending on the amount of aminoplast used, these properties can be varied within a wide range. For example, a certain permanent fold can be achieved with a minimal amount of an aminoplast that hardly adversely affects other properties such as tensile strength or abrasion resistance. If you use larger amounts of an aminoplast, take the Resistance of the permanent fold and the easy-care properties to, but with a correspondingly larger loss for example the tensile strength and abrasion resistance occurs. So the effective amount of an aminoplast is that which is necessary to arrive at a good finish of the processed object, to which the impregnated, dried and cured cellulosic textile material is finally processed, for example into easy-care trousers or shirts that require little or no ironing, or non-iron sheets. In other words, this means that the effective amount of an aminoplast is that when using an ACA or AAC mixture to impregnate a cellulosic textile material and, after the impregnated material has dried and hardened, the material made therefrom Textile objects such as items of clothing, handkerchiefs, clothing or tablecloths, crease resistance, easy-care properties, Non-iron properties and permanent folding

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gives properties. However, it is known to every person skilled in the art that the treatment of cellulosic textile materials with ACA or AÄC mixtures also leads to undesirable side effects due to this finish. For example, when _amino: are plastering used in such amounts that the finished article good Pflegeleicht'eigenschaften, good Bügelfreieigens'chaftenj good crease-free properties and good Permanenzfaltung comprise arising as an unwanted side effects, for example, that the products thus treated corresponding lower tensile strength compared to Articles made of the same material without such a finish, have a lower abrasion resistance, a poorer grip and a lower resistance to frosting, i.e. discoloration and abrasion at the edges. ·

An effective amount of an acidic catalyst is understood to mean that amount> which an ACA mixture hardens when the cellulose-containing textile material is impregnated with the mixture, dried and then under hardening conditions either in atmosphere ¹ in clean air or under vacuum such as in a Time of 10 seconds to 3 hours or longer and at temperatures of 25 to 200 ⁰ C is cured. In earlier publications, the required amounts of a catalyst are given in a very broad range, the amounts to be used not only of that

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particular catalyst, but also depend on the aminoplast used. In US Pat. No. 2,825,710, for example, a catalyst concentration of 6 to 80%, based on the amount of resin present in the impregnation bath, is given. Other publications teach add-on levels of up to about 100 % or more so that the effective amount can range over a very wide range.

An effective amount of a compound of the formula I is understood to mean that amount which is present in the impregnation mixture for impregnating a cellulosic textile material and after drying and curing the impregnated Textile material the articles made from it, such as Garments, curtains, handkerchiefs or tablecloths have a better grip, greater abrasion resistance, better Crease recovery capacity or permanent folding, greater tensile strength and better dimensional stability gives and which at the same time leads to significantly less discoloration and abrasion on edges than if comparatively the object made of the same cellulosic material and with a mixture containing no compound of the general formula I has been treated.

An effective amount of the aminoplast in impregnation solutions for treating paper is that amount which is after

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Impregnating the cellulosic paper and then _; Drying and curing of the paper gives the paper finished in this way greater water resistance compared to untreated paper.

The invention is explained in more detail below with reference to the examples. The tests carried out in the examples were carried out as follows:

characteristic

Suppleness crease assessment shrinkage during washing tensile strength Tensile strength, shear strength, crease recovery capacity

Color fastness when * scouring (frosting) chlorine damage Bow arm rating

Test method AATCC 124-1969 - ■ '' AATCC 88C-I969 'AATCC 135-1970 ASTM D 1682-64 (Grab)', ASTM D 1424-63 (Elmendorf) ASTM D 1175 ~ 64T (Stoll) ASTM D I295-6OT ( Monsanto)

AATCC I2O-I97O AATCC 92-1967. AATCC I24-I969

(Appearance of Durable, Press Fabrics After Repeated Home Launderings, Washing and Drying Procedures IIB) '

AATCC 88C-1969 permanence fold assessment

(Appearance of Creases in Wash-and-Wear Items, After Home Laundering, Washing and Drying Procedures IIIC) except that the wash water temperature was 49 ° C. --It- .;. - ■ · ■■. _; .- '

Chlorine retention AATCC 92-1967

(Chlorine Retained)

309 81971044

Loss of Tensile Strength: One-Sample Procedure

pH of the substance AATCC method 8I-I969

(pH of the water - extraction from bleached textiles) Wet tensile strength and breaking strength

of ASTM D 829-48 paper

example 1

1 mole of freshly distilled methyl lactate was treated for about 3 hours with stirring at a temperature of 20-30 ⁰ C with 2 moles of a 28 #igen aqueous ammonia solution. The mixture was then connected to a full water jet pump vacuum (suction filter pump) at about 70 ° C. to remove water and unreacted ammonia. The resulting lactamide had a purity of about 91 %. With a single reaction, a yield of 97 % of theory was achieved.

The amides of, for example, glycolic acid, ß-hydroxypropionic acid, ß-methoxypropionic acid, o ^ -metboxypropionic acid, o ^ -n-butoxypropionic acid, Methoxyacetic acid, ethoxyacetic acid and oi-iso-propoxypropionic acid shown in high purity and good yields.

The methyl lactate was reacted with metallic sodium to form the alkoxide, which was reacted with methyl iodide to form of methyl 06-methoxypropionate was reacted. A Part of this compound was used to make 06-methoxypropionamide used.

309819/1044

According to the procedure just described, the in
the reactions indicated in Table IA carried out:

n-butyl
iodide Xethyl
iodide IA redistribute
works too Tabel Methyl-ß-hydroxy methyl
propionate iodide Isopropyl
yodid End product o ^ -Methoxy-
propionamide Starting compounds (except Na) Methyl glycolate Methyl-e £ ~
n-butoxy,
propionate ß-methoxy
propionamide Methyl lactate Methyl lactate Methyl-ß-
methoxy
propionate ot-fithoxy-
acetamide Methyl o ^ -
ethoxy-.
acetate oi-isopropoxy-
propionamid Me thy 1 -o6-
isopropoxy
propionate

Example 2 '

The general procedure described in Example 1 was followed
Implementation of the reactions given in Table IB below are used. The products of the process were generally of very high purity; the yields were good.

3 0981 9/1 04-4

Table IB

Ester

Ami η

substituted amide

Methyl lactate

CH, (CH ₃ O) CHCOOCH ₃ CH ₃ O.CH ₂ CH ₂ COOCH ₃ CH ₃ CH ₂ (CH ₃ O) CHCOOCH ₃ CH ₃ (CH ₂ ) ₃ O (CH ₃ ) CHCOOCH ₃ methylamine

Dimethy1amiη

Methylethylamine

Monoethanolamine

Diethanolamine

(CH ₃ ) ₂ NH

CH ₃ CH ₂ CH ₂ .NH.CH ₃

CH ₃ CH (OH) CONH (Ch ₃ ) CH ₃ CH (OHJCON (CH ₃ ) ₂ CH ₃ CH (OH) CON (CH ₃ ) C ₂ H ₅ CH ₃ CH (Oh) CONH (CH ₂ CH ₂ OH) CH ₃ CH (OH) CON (CH ₂ CH ₂ Oh) ₂ CH ₃ (CH ₃ O) CHCON (CH ₃ ) ₂

CH ₃ O.CH ₂ CH ₂ CON (CH ₃ ) CH ₂ CH ₂ CH ₃ C ₉ Hj _{-NH 9} CH ^ CH ₉ (CH, 0) CHCO NHC _o H _k

CH ₃ (CH ₂ ) ₅ NH. C ₂ H ₅ CH ₃ (CH ₂ J ₃ O (CH ₃ JCHCON (C ₂ H ₅ J (CH ₂ J ₅ CH ₃

cn co co -α cn

Example 3

Further compounds of the general formula II were prepared according to the general method described in Example 1, but in these cases piperidine, morpholine and pyrrolidine each instead of ammonia with methyl lactate., Methyl β-hydroxypropionate, methyl glycolate, (CH,) - pC ( OH) CH ₂ COOCH, and HO (CHp), COOCII- were converted. The yields were good to very good and the reaction products were of excellent purity.

Example `` ¹ y

Aniline was heated with a large excess of lactic acid for about one hour at a temperature of 105 ° C. in a fractionating flask while distilling off the water formed. The mixture was then cooled and with a lot. Ice water diluted, whereby the anilide precipitated, which was filtered off, washed with water and dried in the air. The final product CH ^ CHOPICONHCgH ₁ - was of excellent purity. The yield was over 75 % of theory when the molar ratio of lactic acid to aniline was about 10: 1 and when the anilide was precipitated using about 15 volumes of ice water per volume of the reaction mixture.

This process was used to make other anilides of, for example, the following acids such as o ^ -methoxypropionic acid,

309 8 19 / 1OU

tZ-ethoxypropionic acid, glycolic acid, methoxyglycolic acid, ß-methoxypropionic acid, ß-isopropoxypropionic acid and <^ - hydroxybutic acid used, whereby the corresponding anilides were obtained in excellent purity.

Example 5

The method described in Example Ί was used to prepare CH ^ CHOHCON (CgHf-) ρ in excellent purity and with a yield of over 70 % of theory. Numerous compounds of the general formula R ₃ OC (R ₁ ) (R ₂ ) (CH ₂ J _x CON (CgH ₅ ) ₂ can be prepared by using diphenylamine instead of aniline if, for example, the lactic acid is replaced by the following acids becomes: o £ -methoxypropionic acid, ß-methoxypropionic acid, ^ -n-butoxypropionic acid, (CH ₃ J ₃ CCH (OH) COOH or (CIO ₂ CHCh (OCH ₃ ) COOH.

Example 6

After that described below by Einhorn (Ann. 1908, 36I, 113) indicated procedure was N-methylol-lactamide in excellent Quality made:

20 mol (1886 g) lactamide (purity about 9 ^, 4%) were added to an aqueous Porrnaldehydlösung (g 3 ¹ ILO, 37% HCHO) was added with stirring at room temperature. The pH was adjusted to 7 by adding 20% aqueous NaOH. To increase

309819/1044

the pH to 10 25 g of solid potassium carbonate added, the mixture was then cooled for two hours at 60 to 70 ⁰ C.gerührt, to about 25 ° C and adjusted by adding sulfuric acid to pH. 7 The mixture was then filtered, the filtrate (5151 g)> referred to as solution # 6 having a free HCHO content of 14.6 % . Solution # 6 then became the second. Times. -Added with 20 mol of lactamide and repeated the process just described. The oil leakage of the mixture, designated Solution No. 6A, (67IO g) contained 2 % free HCHO and about 37 moles of N-methylol-lactamide.

By replacing that used in the Einhorn method Lactamide by other amides given in Table 2 were further N-methylolamides with excellent purity and in good to excellent yields obtained:

Table 2

Amide "■" '.' - N-methylolamide

HO-CH ₂ CH ₂ CONH ₂

CH ₃ O-CH ₂ CH ₂ CONH _{2 3222}

₀ C H ₁ -O (CH,) CHCONH _{0 0} C H ₁ -O (CH,) CHCONH .CH ₉ OH

CH ₃ O (CH ₃₎ CHCONHPh CH ₃ O (CH ₃₎ CHCON (Ph) CH ₂ OH

HO-CH ₂ CONHCH ₃ 'Hq-CH ₂ CON (CH ₃ ) CH ₂ OH

HSO ... (CH ^) CHCONH ₀ Na.SO, ', (CH, 5CHCONH (CH ₅ OH) *

* In this case, instead of Ba (OH) _? worked in the Einhorn method with NaOH, since acidification replaces the sodium with hydrogen.

309819/1044

Example 7

1 mol of lactohitrile CH ₃ CH (OH) CN and 200 ml of dioxane were mixed and 98 g of concentrated sulfuric acid were added over the course of 5 minutes. The mixture was then left at a temperature of about 80 to 83 ° C. for 4.5 hours. Small amounts of a precipitate formed during this, which was obtained by filtration. The Piltrat was then poured into about I50 ml of dioxane, and the oily layer which forms at the bottom essentially containing the product was recovered by removal of the dioxane under reduced pressure and at a temperature of 75 to 8O ⁰ C. The end product,

That is, (CH,) CHCONHp was obtained in excellent purity and in very good yields (95 % of theory after a single conversion).

When replacing the lactonitrile with a nitrile of the general formula OH-C (R ₁ ) (R ₂ ) - (CH ₂ ) _X CN in the process described above, several sulfated amides of the general formula HSOj,.

manufactured, such as ₅ . CH ₂ CH ₂ CONH ₂ ,

HSO ^ .C (CH ₃ ) (C ₂ H ₅ ) CH ₂ CONH ₂ and (C ₂ H ₅ J

The compound "O ₃ SOC (R ₁ ) (R ₂ ) - (CH ₂ ) _X CON (R _{1 |} ) (R ₅ ) is a sulfate ester of a hydroxycarboxamide. This ionic formula shows that when the ester is used in one acidic

309819 / 10U

The negative charge is compensated by a hydroxonium ion and that when the ester is used in an alkaline medium or neutral medium, this is present as a salt, in that the neutral

negative charge through a suitable cation such as Na, K, NH ₁ . or 1/2 approx .. These salts will result in an acidic or neutral reaction in water, depending on the dissociation constants of the acid used and the corresponding base such as KOH or NH _{1 .OH in water.}

Example 8 . . ■.

The following aqueous solutions were produced: -

A ^ Dimethyloldihydroxyethyleneurea (DMDHEU) as a solution with a content of * J5 % solids through the reaction of urea with glyoxal and methylolation of the product with formaldehyde. (Existing formaldehyde excess 7.1 %)

B: _ N-methylolactamide (NML) solution with a solids content of 72 % from lactamide and formaldehyde.

Cj_ zinc nitrate solution (solids content 50 %) ■ ' Pj_ lactamide solution (solids content 70 %) ·

Then the following ACA and AAC mixtures became as follows manufactured:

3 0 9 819/1044

8a (usual ACA) by mixing A with a content of
30 parts of pesticides and C containing 6 parts

8b (ACA mixture) by mixing B containing 5 parts of solids and 1/4 of the above δΑ mixture.

8C (ACA mixture) by mixing A containing 7.5 parts of pesticides and B containing 5 parts and then adding C containing 1.5 parts
Share Zn (NO) ₂

8D (AAC mixture) by mixing A with a content of 30 parts of pests and B containing 20 parts of pests.

8E (ACA mixture) by mixing C with a content of

1.5 parts Zn (NO ) ₀ and 1/4 of 8D.

8p (ACA mixture) by adding D containing 6 parts of lactamide to 1/4 of 8A.

Another mixture 8G was prepared by using 4.6 parts of water and 10.7 parts of CH ₃ (HSO ₁₁ ) CH ^ ONH _{2 in} place of D in solution 8p.

Example 9

An approximately 76 χ 38 cm sample of 41OW worsted batiste shirt fabric, So a cellulose-containing shirt fabric, was

309819/1044

immersed in the mixture 8A up to a moisture absorption of approx. 81 % after the solids content of the mixture 8A had been adjusted to 9% by adding water. The sample was then clamped to fix the shape and size in a frame, cured for 5 minutes at 93 ° C and then dried for 5 minutes at 163 ⁰ C. This sample was named Sample No. 9A.

In five further attempts IXB to IXG were according to this procedure Fabric samples treated, with .but instead of the mixture 8a the solutions given in Table 3 were used.

Diving boats Table 3 Sample no. example 8B Solids content in % '9B IXB 8C 12.7:, "V 9C. IXC 8D ;. ■ · ■■■■■ 13.8 9D IXD * ■ 8E 13.9 9E IXE 8F . 1 ^, 0 9F IXF 8G 1.3.8 9G . IXG 12.9

cured in SO ₂

Example 10

Samples 9A and 9B were as shown in Tables 1 and 5 examined. When examining samples 9C through 9G results were very similar to the "investigation of the Sample 9B obtained.

3 098 19 / TOU

'Tensile strength 160 Chafing
strength Table 4 After chlorine damage
(Tensile strenght 5 washes
) (Elmendorf)
Chain shot 208 chain Evaluation of the
Non iron chlorinated and %
burned out chlorinated Loss of
Tensile strength sample 272 55 after
5 washes 29 29 0 9A
C *) 368 127 3.8 44 7 90 §3 3 CO co O
J * · Table 5

Crease recovery
fortune before
To wash Wrinkle recovery
fortune after
5 washes chain Row comb 2.5 cm Tensile stress
availability toughness Shot sample dry damp dry damp 24
34 % Receipt of
tensile strenght
of the untreated
of the fabric Shot strain
Chain shot chain 113.7
247.5 "9A
9B 296 259
288 241 288 250
276 256 47
67 13th
25th 3.8 17.5
4.4 19, .5 45.6
74.8

Example 11

Λ) Several meters of cellulosic corduroy were impregnated with a state-of-the-art ACA mixture HA. The aqueous dimethylol-dihydroxyethylene urea solution contained 18% pesticides and about 1% zinc nitrate, about 3> 0 % of a nonionic polyethylene emulsion and about 0.1 % of a nonionic wetting agent.

The corduroy took up about 68.5 % of its weight in solution in the diving fleet. The fabric was then dried for 5 minutes at 93 ° C, cut, ironed and cured. The ironing took place on a head press with a head temperature of 175 ° C. The fabric was then steamed for 30 seconds, exposed to vacuum for 30 seconds without the application of heat or tension, then cured at 175 ° C for 15 seconds under pressure and then cured at 160 ° C for 5 minutes in a hot-air oven . This sample was named Sample HA.

B) The procedure described for sample HA was using the inventive ACA mixture HB, which by mixing B from Example 8 with HA to achieve 5.3 parts of B pesticides in HB was obtained repeatedly. The swatch was designated as Sample HB.

309 8! 9 / 10U

- I ₁₂ -

The swatches HA and HB were examined; the results are compiled in Tables 6 and 7.

Sample HA HB

Tabel

Crease recovery ability before washing

dry damp

309 302

284 288

Tensile strength
Row comb 2.5 cm

chain
6l

Shot
24
31

Tabel

Tensile strength (Elmendorf)

Sample chain HA HB

1 * 172 2144

Shot 640 928

Abrasive

firm-? ®eiei ™

Chain 5 washes

386, 4.3 1133 4.5

Evaluation of the

immediately after 5 washes 5.0 5.0 5.0 5.0

example

A) A state-of-the-art ACA solution, called Solution A12, was prepared by adding 152 g water, 208.5 g ethylene urea and 492.5 g aqueous 37% formaldehyde solution were mixed. The pH was adjusted by adding

309819/1044

20 # aqueous sodium hydroxide solution adjusted to 7, the temperature ^{rising to about 40 0} C *. Then 6 g of K ₂ CO, were added, the pH rising to 9 * 9, and the temperature rising to about 55.degree. The mixture was then about 1 hour at £ e wa heated 60 C and then adjusted after cooling to 25 ⁰ C by addition of 50 #iger aqueous sulfuric acid to a pH value of 7>. 2 A gummy precipitate formed which was filtered off. The filtrate, that is a -AAC mixture corresponding to the state of the art, was mixed with 52 g of Zn (NO ..) ₂ to produce an ACA mixture.

B) Another ACA mixture corresponding to the prior art, referred to as solution 12B, was prepared according to the method described under A), but instead of the ethylene urea 238 g propylene urea and 483 g formaldehyde solution and 149 g of water were used.

C) An ACA mixture according to the invention, called solution 12C, was prepared using the methods described for the preparation of solution A. produced, but 108 g of lactamide was added to the mixture became.

D) Another AGA mixture according to the invention, solution HD, was prepared by the method described for HC, wherein

309819/1044

but instead of the ethylene urea 238 g propylene urea and 83 g formaldehyde solution, 106 g lactamide and 1 * 19 g Water were used.

Example 13

Following the procedure described in Example 9A), solutions 12A to 12D were used in those given in Table 8 Quantities of fabric samples measuring approximately 76 χ 38 cm Impregnated and cured from 100 tiger cotton sheets. These samples were named Samples I3A through 13D.

Diving fleet Table 8 Sample no. example 12A
12B
12C
12D Solids content in % 13A
13B
13c
13D XIIIA
XIIlB
XIIIC
XIIID 9
13.25
13.25
13.25

The samples were examined according to the procedures given; the results are compiled in Tables 9 and 10:

309818/1044

Table 9

Ir.:.-rcrer.-.cls-· Kr.ittererhcls- "emcrrsn before the ability after washing, 5 vials tensile strength ranked 2.5 cm elongation toughness

brooken moist I rrocker. . wet

282

! 291
260
, 270

% Receipt; the
tensile strenght
weft of the untreated warp

'52

261

Oil

18th

21

43
42

Chain shot

20.0

4.6 19.0 68.0 175.0

Chain shot

71.0 180.0 '■

Table 10

ißfesii ^ ity (V Irner.dcrf) For see I'lstte Shot i: a ■ 352 192 13 = '350 187 ire 604 ■, 817 ■:. ID 817 770

Abrasion resistance chain '

Evaluation of the ironing properties
after 5 washes

2.5
3.0

co --J cn

Example 14

The procedure described in Example HA was repeated, but the solutions HA to HD were diluted to a PET content of 13% before use. The treated swatches were designated as Samples 14A through 14D; the results of the investigations are summarized in Tables 11 and 12:

Knittor relaxation ability before washing

Table 11

Crease recovery

fortune after

5 washes

Row comb 2.5 a

sample dry dry chain Created; l'IA 309 284 61 24 14B 300 290 55 20th 14C 302 281 68 31 I'll) 295 283 67 32

Table 12

Pro ΐΜί

14Λ I'IB l'lC I4l)

Tensile strength rating dor

(E lmondqrf) Abrasion resistance Bilge 1; i rmc. If.en.schaf t

1472

1 'u> I

2 144

640

il'iO

Shot

386

.568

.115 5

1027

') 0 9 0 19 / I 0 / »/»

Example 15

A) A prior art ACA solution, "solution 15A", was prepared by mixing 120 g _s urea were dissolved with stirring in 1650 g water. While stirring, 5 portions each containing 58 g of aqueous glyoxal solution and 1 g of sodium carbonate were added. After each addition the pH was k; 5. After the total amount of glyoxal and sodium carbonate had been added, the pH was adjusted to 5-5 by adding 20% aqueous sodium hydroxide solution. The mixture was then heated to 50 ° C. for 90 minutes, and after 5 minutes at this temperature the pH had dropped to 5.3 and was readjusted to 5 »5 by the dropwise addition of sodium hydroxide solution, so that at the end of the heating period the pH was 5 * 5. The mixture was added after cooling to ⁰ C with 2.5 g of aqueous 37 568 #iger formaldehyde solution, the pH is adjusted by adding dilute sodium hydroxide solution 5 »85 and the. The mixture was then heated to 50 ° C. ^{again for 1.5 minutes.} After the mixture had cooled to 25 ° C., 82 g of Zn (NO ^) _{2 were} dissolved in it as an acidic catalyst.

B) An ACA mixture according to the invention, "Solution 15B", was like described under A), but the aqueous urea solution was additionally mixed with 89 ε lactamide.

309811/1044

Example l6

A) A shirt fabric as in Example 9A was impregnated with solution 15A after dilution to a pesticide content of 10 % with water up to an 80% absorption of the immersion liquor and then stretched in a frame to fix the size and shape. After 5 minutes drying at 90 ⁰ C and 5 minutes cure at 165 ° C was designated as a sample, the sample L6A.

B) The procedure described under A) was repeated using solution 15B after dilution with water to a pesticide content of 12.5 % instead of solution 15A. The cured sample was named Sample 16B. The test results for samples 16A and 16B are summarized in Tables 13 and I ^:

Crease recovery
fortune before
To wash -
to the Table 13 Row comb 2.5 cm dry Crease recovery
fortune after
5 washes chain Shot sample 281
268 dry 98
100 v \
37 16A
i6b 25 *}
2 ^ 5

309819/1044

Tabel

Tensile strength ■. Evaluation of the

(Elmendorf) Abrasion resistance, iron arm property.

after 5 washes

Sample chain weft weft

16A 13 ¹ J * i ' 896- 151.' 3, CHIOS 15Ö'4 102 ^ '2il5'. 3.5 +

Example 17 -

A) A prior art aqueous aminoplast solution for paper treatment, "Solution I7A", was prepared by dissolving 8.6 g of ethylene urea in 200 g of water and then adding 2 * 1.3 g of a 37 # aqueous urea solution . The mixture was 1/2 hour at 6O ⁰ C is heated, and then 2 cooled 5 C, after which the pH was 5.0.

B) The method described under A) was repeated, but prior to the addition of the formaldehyde the ethyleneurea "solution with H, 5 g of lactamide was added. This aminoplast invention for paper treatment was referred to as" solution 17B "and had a pH of 4.2 on.

C) The procedure described under B) was repeated using 8.9 g of lactamide instead of 4.9 "g.

3 0 a 8 i 9/1 0 U

BATH ORIGINAL

inventive finished solution, "Solution 17C", had one pH 4.1.

D) A prior art aqueous aminoplastic solution for paper treatment, "Solution 17D", with a pH of 5.0 was prepared by dissolving 2 g of Zn (NO ^) ₂ in a sample of solution 17A.

E) An aqueous paper treatment solution according to the invention, “solution 17E”, with a pH value of 5> 0 when measured at 25 ^° C., was prepared by dissolving 2 g of Zn (NO,) ₂ in a sample of solution 17B.

P) A further aminoplast paper treatment solution according to the invention, "Solution 17F", with a pH of 5> 0, was done through Dissolve 2 g of Zn (MO) in a sample of the 17C solution.

Example 18

Cellulose-containing pilgrim paper sheets (Whatman IJo. 1) were impregnated separately with solutions 17A to 17F after adjustment to a pesticide content of 15 % solids and then squeezed off with a 10.5 kg brass roller to remove excess liquid, dried and at Hardened at 105 to 110 C. The samples produced in this way were as

3008 197 1OM

Samples 18.A to! Β! ' designated. The dry strength and wet strength according to ASTMD-829 'of Samples 18A through 18F were determined; the results are summarized in Table 15:

Table 15 ^l '· \

Strength in kg / cm wet strength, sample moist dry V frown strength

iBk 0.03 18B ■■: i.i.5- iac 1.19 18D 1.01 18e 0.90 18F 0.78

1.26 _v - 2i5 2.38 - HB

Obtained Xm iwesentlichen same Resultateiviuriäen when {a) in place of V ^ n Kthylenharnstoff Dihydroxyathylenharnstoff barren 'propylene urea; (b) instead of tactamid N-methylolactamide, CIUCHÖH.GO.NE.GH ,, CH, CHQH.GO; NH.CH ₅ CH ^ OH, 'CH.CHOH.CO, NH.Ph, /

, CH-CHOH.CC * .NC ^ f
^ '■■■■ ■■; ■■■■ ^

, HO.CHgCHg.GO »NH _{2 were} used. Even if (c) lactamide or one of the other compounds mentioned under (b) were added to an amino plastic solution prepared from formaldehyde and ethylene urea, propylene urea or dihydroxyethylene urea, excellent results were obtained. ; ^'::. "- ...

• ^; ■■■■■■. "■. ■ '..., ■■■" - ■; ■ \ -. ■■; ,, '".;,". '-V ■. "■

Example 19

A) 103 gc £ -hydroxy-n-butyramide (1 mol) was added with stirring 1 mol of a 37 iigen aqueous formaldehyde solution mixed. The pH was adjusted to 7 by adding 20 # aqueous sodium hydroxide solution, then 1.25 g of sodium carbonate were added added and the mixture heated to 60 ° C for two hours. After cooling to room temperature (approx. 25 ° C) the The mixture is adjusted to pH 7 by adding sulfuric acid and filtered off, an aqueous N-methylol-O6-hydroxy ~ nbutyramide solution, "Solution 19A" was obtained.

B) to G) Following the procedure described under A), six additional solutions were made using one each Moles of various hydroxyamides given in Table 16 were prepared:

example

XIXB XIXC XIXD XIXE XIXF XIXG

Tabel Amide 16 N-methylolamide
in solution Ch ₃ CHOHCONH ₂ 19B (CH ₃ J ₂ C (OH) CONH ₂ 19C CH ₃ CHOHCONHCh ₃ 19D CII ₃ CiIOHCONHCH ₂ CII 19E CIL ₇ CUOIICONIi (CH ₂ ) 2 ^0H 19p HIGH _n COHIU 3CI ₃ 19G

309819/1044

Example 20

The solutions 19A to 19G were each mixed separately with an aqueous "dimethylolethyleneurea solution (DMEU45 %) , so that a molar ratio of N-methyl.ol-o ^ -hydroxy-n-butyramide to DMEU of 1: 1, 3. After dilution with water, zinc nitrate and a nonionic wetting agent (polyethylene glycol phenyl ether) were added to the mixtures, so that an ACA mixture was obtained with the following content: DMEU 7.5 % _a Zn (NO,) ₂ 1.5 J >, non-ionic wetting agent. O- $ l '%. The molar ratio of N-methyl-ol-o ^ -hydroxy-n-butyramide: to DMEU was adjusted to 1: 1.4 and the pH value, by adding' IG% acetic acid adjusted to 5 to 6, so that ACA immersion liquors, "Solutions 20A to 20G", were obtained.

Ex ie 21 l - '.

Samples of cotton comb yarn batiste with the dimensions of about 7 6 χ 38 cm were impregnated with the solutions 20A to 2OG up to a moisture absorption of 80 %. The. Cured samples were stretched after treatment in the dip liquor in frame, to obtain the form and size *, then 5 minutes at 93 ° C and then dried for 5 minutes at 163 ⁰ C. The cured samples were designated Samples 21A through 21G and examined. The results are compiled in Table 17.

3 09819/1 OiA

Table 17

sample Series of strips tensile strength a η g s after 5 To wash Abrasion resistance after 5 washes Chlorine damage valuation
the coat hanger Con
trolls
2IA a η f Shot chain Shot at first chain completion
% Firm
loss of life free own 213 chain 18th
23 26th
31 20th
27 chain 107
202 7th scnaiten
η. 5 washes «*»
O
4P
«Α 21C 28
33 27 32 2k 151
184 ' 230 0 3.5
3.5 «Α 21D 30th 22nd 28 23 192 179 - 3.5 O 21Ξ 32 25th 30th 23 165 278 7th 3.5 Century * 21? 32 20th 32 18th 251 13.1 3 3.5. 21G 32 20th 27 23 116 203 - 3.5+ 30th 26th 31 26th 208 241 3.0+ 31 259 3.0+

CJI CJ CO

In the table, “control” is understood to mean a material sample which was treated in a similar manner to samples 21A to 21G, but with a dip tube with a content of 7.5 % DMEU; 1.5 % Zn (NQ- ,) _? and 0.1 % of a nonionic wetting agent had been used, the pH of which was adjusted to 5 to 6 by adding 10% acetic acid.

Example 22. - .-; "" - ■ - ". _: ■ · -...

The method described in Example 21 was repeated, but using the ACA mixtures from Example 20 according to the invention the corresponding amides and instead of the M-methylolamides used in Example 20 were used, the Molver- " ratio of amide to DMEU was 1: 1.4. Examination of the treated fabric samples showed essentially the same values as iri Table 17 using the corresponding N-methylolamides,

Ex iel 23

A) A ÄAC mixture according to the invention, "solution 23'A", 'was prepared by mixing 2.4 mol propylene urea, 150 β water, 1 mol methyl lactate and 3 mol ammonia ... The mixture was kept for three hours in a closed vessel heated to about 90 to 95 ° C., then the excess ammonia was removed by purging with nitrogen at a temperature of 90 to 95 ° C. for one hour. Then, ¹ 1.5 mol of formaldehyde in the form of an aqueous ¹ were #ige IO) i -, 'solution was added and the pH #iger by the addition of aqueous sodium hydroxide solution .25-

8197104

set to 9. After leaving it at about 65 ^° C. for one hour, the pH of the mixture was then adjusted to 7 by adding 20% strength aqueous sulfuric acid.

B) An ACA mixture according to the invention, "Solution 23B", was passed through Addition of 38 g Zn (NO) "half of the solution 23" obtained.

C) A state-of-the-art AAC mixture, "Solution 23c ", as under A) with omission of the methyl, lactates produced.

D) A state-of-the-art ACA mixture, "solution 23D", was made halfway by adding 38 g of Zn (NO,) p of solution 23C.

Example 2'J

Diving liquors were prepared by diluting solutions aer 23A to 23D with water to the specified in the table l8 solid content:

Table 1 8 Feetηtoff content in % diluted solution Diving fleet 12, ü
l'l
7, ¹ y
9.0 23Λ
23B
23c
? w 2'ΙΛ
2'IB
2'IC
2'U)

309819 / 10U

Example 25

A) A sample of a cellulosic shirt fabric with the Dimensions of about 7.6 x 38 cm was impregnated with the solution 2 ^ A up to a moisture absorption of 82 $, then to the Fixation of shape and size in a frame, dried for 5 minutes at 92 ° C and 5 minutes at 16.5. G in Cured sulfur dioxide. The sample was named Sample 25A designated.

B) A swatch, designated Sample 25B, was made as under A), but replacing the solution 2 * JA with 2 * JB and curing was done in air.

C) Sample 25C was as under A) using the solution 2IjC prepared instead of solution 24A. ■

D) The procedure described under B) was repeated using solution 24D instead of solution 2'JB, the Sample of fabric designated as Sample 2 | 5D was obtained. Samples 25A to 25D were then examined; the results are compiled in Table 19:

ίο /

Table 19

τ 255 . "Θx * nc2 ^^ - vcr
ν Ci * 7 '^ ** ^ Λ ¹ ^ * deni tensile strenght Shot Tensile strength
(Elir.endorf) Chafing
strength Evaluation of the 25C trek Row comb 2.5 cm Chain shot chain Non iron 25D chain 22nd 5 washes 295 42 1.71 1.2 1800 co 293 56 21 1.8 1.7 2200 3.0 id 275 47 13th 1.41 0.81 509 3.0 237 52 1.41 0.81 306 3.0 44 3.0

Substantially the same results as in Examples 25A and 25B were obtained when the methyl lactate used in Example 23A by-ethyl lactate, methyl-6 -hydroxy-n-butyrate, ethyl-0 ^ -hydroxy-n-butyrate or Methyl-06-hydroxy-isobu.tyrate was replaced. The corresponding solutions were used as in Example 2k for the production of immersion liquors and the immersion liquors were used as in Example 25 corresponding to 25A for AAC immersion liquors and 25B for ACA thawing liquors »

Example 26 _; ■

Handle ratings for a number of swatches are summarized in Table 20 below. For this, the ASTM definition of the handle (Book of ASTM Standards, 1965, part 2 ^l \ ₎ page 712) was used. In Table 20, the rating number means 1 bad hand, 2 moderate hand, 3 good hand, and ¹ excellent hand.

sample

9A

9B

HA

^; HB

13A

13B

13c

In the

3ö9 819 / 10'44

Table 20 handle 2 2 I _{1 +} 2 2 3 3 2 2

Prob e 1'4C

I'm 16A 16B 21A 21B

21D

3 U 9 B 1 9, '1 0

2 3 3 3

21C "/,

21E, I,

21P 3

21G j,

25A ■ i,

25B ι,

25C ₂

25D ρ

Claims (1)

Patent claims 1. Aqueous finishing solution, characterized by a content of aminoplasts, a compound] of the general formula I. (R ¹ ) (R ² ) (R ³ O) C (CH ₂ ) _x COM (R ^{i |} ) (R ⁵ ), ' 12th
in which the groups R and R can be identical or different and hydrogen atoms or C to C ₁ - alkyl groupsi R is a hydrogen atom, a C. to C ^ alkyl group, a • 4 —SO—, H group or its salt, χ equal to 0 or 1, R a Hydrogen atom, a phenyl, ß-hydroxyethyl or C. bis CT Cn-alkyl group, and R is a hydrogen atom or a phenyl, Ilydroxymethyl, ß-hydroxyethyl or C. bis Co-Alky! Group 4 5 mean, or in which R and R together with the nitrogen atom a heterocyclic piperidino, morpholino or pyrrolidin-1-ylinoring. form, where, when R and R together with dem.Stickstoffatom form a heterocycle, R is a hydrogen atom, and optionally to an acidic one Catalyst suitable for hardening the aminoplast, .wherein the mixture preferably 5 to 75% by weight of the aminoplast contains. 2. A method of making a finishing solution according to claim 1, which are essentially no acidic catalysts ; ϊ ο π S ι μ / 1 η contains, characterized in that a mixture containing an aminoplast precursor, aqueous formaldehyde and a compound of the general formula I, where the Equivalent ratio of aminoplast precursor to formaldehyde is 1: 1.1 to 2, converted to form the aminoplast and the pH of the mixture is adjusted to 6.5 to 7. 3. The method according to claim 2, characterized in that the pH of the mixture before the formation of the aminoplast 8.5 to 10.5 is set. H. Process for the production of a finishing mixture according to claim 1, which contains essentially no acidic catalyst, characterized in that a mixture containing an aminoplast precursor, water, ammonia and a compound of the general formula II (R ¹ ) (R ² ) (HO) C (CH ₀ ) COOR ⁶ L- A 1 2 in which R, Π and χ have the same meaning as Ln of the formula I, and in which R * _{denotes a C. to C r} -alkyl group, where da :; molar ratio of the compound of general formula II: u ammonia about 1: 1 to 10, from about 0 [■> to J \ hours at ei nor temperature of 20 converted to 100 ⁰ C, which is not implemented "·.? ; Removed ammonia, the mixture with 9 819/1044 added aqueous formaldehyde, the equivalent ratio of aminoplast precursor to formaldehyde in the mixture being about 1: 1.2 to 2, the pH of the mixture being adjusted to 0.5 to 10.5, the mixture then being 0.25 to 2 hours kept at a temperature of 25 to 190 ^° C. and then the pH of the mixture is adjusted to 6.5 to 7 * - ■ 5, method of making a finishing mix according to Claim 1, which contains an acidic catalyst, characterized in that the pH of a mixture with a Content of an aminoplast precursor, aqueous formaldehyde, and a compound of the general formula I, where the equivalent ratio of aminoplast precursor to formaldehyde 1: 0.9 to 1, adjusted to 5.5 to 10.5, the misehing 15 to 2 ^ 0 minutes at a temperature of 25 to Leave 90 C, the pH of the mixture then forming. the aminoplast is adjusted to 6.5 to 7 and the mixture is mixed with the acidic catalyst, 6. Process for the preparation of a finishing mix according to Claim 1, which contains an acidic catalyst, characterized in that a mixture according to Claim 1, which is im is essentially free of acidic catalysts, with a acidic catalyst. is mixed. 19/1044 7. A method for treating a cellulosic paper, characterized in that the paper is coated with a mixture according to claim 1 which is essentially free of acidic catalysts is, impregnated, the impregnated paper is dried and the dried paper is used to harden the amino plastic heated v / earth. 8. A method for treating a cellulose-containing paper, characterized in that the paper impregnated with a mixture according to claim 1 having a content of 0.1 to 5 wt.% Of an acid catalyst, the impregnated paper was dried and the dried paper to cure the aminoplast is heated. 9. A method for treating a cellulosic textile material, characterized in that the textile material with a mixture according to claim 1 with a content of one acid catalyst impregnated, the impregnated material dried and the dried material to harden the Aminoplast is heated. 10. Process for the production of a finished garment made of a cellulosic textile material, characterized in that the textile material with a mixture according to claim 1 containing an acidic catalyst 309819/1044 impregnated, the impregnated material at a, temperature below the curing temperature of the aminoplast component the mixture is dried, the dried material is cut into the shape of the garment, into a garment sewn, the sewn garment provided with gaps and then for the hardening of the aminoplast and is heated in situ to convert it into the insoluble state. si: kö 3098 19/1044